Methods for collecting time/activity pattern information related to exposure to combustion products

Focus groups, surveys and questionnaires, diaries and observations can be used to gather information about people's exposure to a wide range of combustion products. Information about locations and durations of exposure, and sources of exposure can be obtained with these instruments. The types of instruments used must be fine tuned to meet the design characteristics of the community in which the study will be conducted.     

The role of condensed organic matter in the nonlinear sorption of hydrophobic organic contaminants by a peat and sediments

This study examines the effect of soil organic matter heterogeneity on equilibrium sorption and desorption of phenanthrene, naphthalene, 1,3,5-trichlorobenzene (1,3,5-TCB), and 1,2-dichlorobenzene (1,2-DCB) by soils and sediments. Two estuary sediments, a Pahokee peat (PP; Euic, hyperthermic Lithic Haplosaprist), and two subsamples (base- and acid-treated peat [TP] and acid-treated peat [FP]) of the peat were used as the sorbents. The contents of black carbon particles were quantified with a chemical extraction method. Petrographical examinations revealed the presence of the condensed soil and sediment organic matter (SOM) in Pahokee peat. The Freundlich isotherm model in two different forms was used to fit both sorption and desorption data. The results show that the sorption and desorption isotherms are generally nonlinear and that the apparent sorption-desorption hysteresis is present for phenanthrene and TCB. Detailed analysis of sorption data for the tested sorbent-sorbate systems indicates that black carbon is probably responsible for sorption isotherm nonlinearity for the two sediments, whereas the humic substances and kerogen may play the dominant role in nonlinear sorption by the peat. This investigation suggests that the microporosity of SOM is important for the hydrophobic organic contaminant (HOC) sorption capacity on the peat.     

Real-time, high-resolution quantitative measurement of multiple soil gas emissions: selected ion flow tube mass spectrometry

A new technique is presented for the rapid, high-resolution identification and quantification of multiple trace gases above soils, at concentrations down to 0.01 microL L(-1) (10 ppb). The technique, selected ion flow tube mass spectrometry (SIFT-MS), utilizes chemical ionization reagent ions that react with trace gases but not with the major air components (N2, O2, Ar, CO2). This allows the real-time measurement of multiple trace gases without the need for preconcentration, trapping, or chromatographic separation. The technique is demonstrated by monitoring the emission of ammonia and nitric oxide, and the search for volatile organics, above containerized soil samples treated with synthetic cattle urine. In this model system, NH3 emissions peaked after 24 h at 2000 nmol m(-2) s(-1) and integrated to approximately 7% of the urea N applied, while NO emissions peaked about 25 d after urine addition at approximately 140 nmol m(-2) s(-1) and integrated to approximately 10% of the applied urea N. The monitoring of organics along with NH3 and NO was demonstrated in soils treated with synthetic urine, pyridine, and dimethylamine. No emission of volatile nitrogen organics from the urine treatments was observed at levels >0.01% of the applied nitrogen. The SIFT method allows the simultaneous in situ measurement of multiple gas components with a high spatial resolution of < 10 cm and time resolution <20 s. These capabilities allow, for example, identification of emission hotspots, and measurement of localized and rapid variations above agricultural and contaminated soils, as well as integrated emissions over longer periods.     

Soil and litter phosphorus-31 nuclear magnetic resonance spectroscopy: extractants, metals, and phosphorus relaxation times

Phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy is an excellent tool with which to study soil organic P, allowing quantitative, comparative analysis of P forms. However, for 31P NMR to be tative, all peaks must be completely visible, and in their correct relative proportions. There must be no line broadening, and adequate delay times must be used to avoid saturation of peaks. The objective of this study was to examine the effects of extractants on delay times and peak saturation. Two samples (a forest litter and a mineral soil sample) and three extractants (0.25 M NaOH, NaOH plus Chelex (Bio-Rad Laboratories, Hercules, CA), and NaOH plus EDTA) were used to determine the differences in the concentration of P and cations solubilized by each extractant, and to measure spin-lattice (T1) relaxation times of P peaks in each extract. For both soil and litter, NaOH-Chelex extracted the lowest concentrations of P. For the litter sample, T1 values were short for all extractants due to the high Fe concentration remaining after extraction. For the soil sample, there were noticeable differences among the extractants. The NaOH-Chelex sample had less Fe and Mn remaining in solution after extraction than the other extractants, and the longest delay times used in the study, 6.4 s, were not long enough for quantitative analysis. Delay times of 1.5 to 2 s for the NaOH and NaOH-EDTA were adequate. Line broadening was highest in the NaOH extracts, which had the highest concentration of Fe. On the basis of these results, recommendations for future analyses of soil and litter samples by solution 31P NMR spectroscopy include: careful selection of an extractant; measurement of paramagnetic ions extracted with P; use of appropriate delay times and the minimum number of scans; and measurement of T1 values whenever possible.     

Changes in the rhizosphere of metal-accumulating plants evidenced by chemical extractants

The plants Salix viminalis L. (common osier) and Thlaspi caerulescens J. Presl & C. Presl have been studied often because of their high potential to extract heavy metals from soils. The soil properties favoring this phytoextraction are not yet fully known. In this study we compared three frequently used single-extracting agents (NaNO3, diethylenetriaminepentaacetic acid [DTPA], and ethylenediaminetetra-acetic acid [EDTA]) with a sequential extraction procedure to describe changes in the different Cd, Cu, and Zn pools in the rhizosphere of S. viminalis and T. caerulescens grown on calcareous and acidic Swiss soils in a pot experiment. The sequential extraction was used to assess the chemical affinities of these heavy metals (HM) in the soil whereas the single extractants were used for estimating the bioavailable HM pools in the soils. Cadmium depletion in several pools was most apparent in the acidic soil, with a significant decrease observed in the NaNO3-, DTPA-, and EDTA-extractable fractions following T. caerulescens growth compared with control pots. The sequential extraction showed that most Cd extracted by the plant from the acidic soil originated from the organic pool, which implies that heavy metals bound to organic matter may constitute a significant part of the bioavailable Cd pool in soils. In the calcareous soil only a small amount of Cd was taken up by T. caerulescens, and this came mainly from the carbonate-bound fraction. This study shows that T. caerulescens, and to a lesser extent S. viminalis, can alter the heavy metal distribution in different soil pools within 90 d.     

Multinuclear magnetic resonance analysis of two humic acid fractions from lowland rice soils

To determine the effects of intensive cropping of tropical lowland rice (Oryza sativa L.) and the associated long-term soil submergence on chemical properties of soil organic matter, we used solid-state 13C and 15N and solution 31P nuclear magnetic resonance (NMR) spectroscopy to analyze the labile mobile humic acid (MHA) and the more recalcitrant calcium humate (CaHA) fractions extracted from a series of soils supporting several long-term field experiments in the Philippines. The soils varied mainly in degree of submergence and cropping intensity, ranging from a rainfed rice field without soil submergence to irrigated double- and triple-cropped fields in which soil remains submerged almost all year long. As reported previously, all analyses associated increasing intensity of rice cropping with larger proportions of less humified material in the MHA and CaHA, such as diester phosphorus (P), amide nitrogen (N), and phenolic carbon (C). We established significant correlations between proportions of various spectral areas as well as between some spectral areas and other humic acid (HA) properties such as visible light absorption and free radical concentration (positive indices of humification) and hydrogen (H) concentration (negative index of humification). For example, spectral proportions of heterocyclic N were positively, and proportions of amide N and phenolic C negatively, correlated with visible light absorption and free radical concentration, and each of these spectral proportions had an opposite sign when correlated with H concentration. The correlations of N-alkyl C proportions were the strongest with these properties and with other functional group proportions.     

Radionuclides as indicators of sediment transport in agricultural watersheds that drain to Lake Erie

An issue in evaluating the success of agricultural management practices is the speed that eroded particles make their way through the downstream waters. In this study at Old Woman Creek (OWC) and Rock Creek (RC), two largely agricultural watersheds in Ohio, the flux of sediment and radionuclides (7Be, 210Pb, and 137Cs) in thunderstorm runoff was examined to better understand transport of eroded agricultural soils. The hydrograph in an agricultural area under no-till was similar in timing, but of lesser magnitude, than the hydrograph from a similar-sized area under conventional tillage. The activities of 210Pb and 7Be are linearly correlated and are higher in suspended sediments derived from no-till subbasins than those derived from conventionally tilled subbasins. A suspended sediment plume, identified by its unique radionuclide signature, was traced through 17 km of OWC stream channel in approximately 13.4 h (0.35 m/s). The downstream exponential decrease of 7Be activities in suspended sediments 3 to 12 h after passage of the sediment plume was used to estimate transport distances of suspended sediment from 2 to 17 km, respectively. Transport distances of suspended sediments were also calculated from wave kinematics and indicate that at OWC suspended sediment transport distances were longer in streams draining areas of no-till (19-26 km) than in the streams draining areas of conventional tillage (6-15 km). Suspended sediments travel 7 to 22 km at RC. The transport distances are long relative to the lengths of the stream channel and indicate that erosion control methods implemented in the watershed should be reflected quickly in downstream waters.     

Influence of manure application on surface energy and snow cover: model development and sensitivities

Winter landspreading is an important part of manure management in the U.S. Upper Midwest. Although the practice is thought to lead to excessive P runoff losses, surprisingly little has been learned from field experiments or current water quality models. We captured knowledge gained from winter manure landspreading experiments by modifying a mechanistic snow ablation model to include manure. The physically based, modified model simulated the observed delay in snow cover disappearance and surface energy balance changes caused by application of the manure. Additional model simulations of surface energy balance estimates of radiation and turbulent fluxes showed that during intense melting events the manure on top of snow significantly reduced the energy available for melt of the snow underneath, slowing melt. The effect was most pronounced when snowmelt was driven by both relatively high solar radiation and turbulent heat fluxes. High absorbed shortwave radiation caused significant warming of the manure, which led to substantial losses in turbulent fluxes and longwave radiation. Simulations of snowmelt also showed that manure applications between 45 and 100 Mg ha(-1) significantly reduced peak snowmelt rates, in proportion to the manure applied. Lower snowmelt rates beneath manure may allow more infiltration of meltwater compared with bare snow. This infiltration and attenuated snowmelt runoff may partially mitigate the enhanced likelihood of P runoff from unincorporated winter-spread manure.     

Natural uranium and thorium distributions in podzolized soils and native blueberry

Plant uptake of radionuclides is one of many vectors for introduction of contaminants into the human food chain. Thus, it is critical to understand soil-plant relationships that control nuclide bioavailability. Our objectives in this study were to (i) determine the extent of U and Th uptake and cycling by blueberry (Vaccinium pallidum Aiton) in native habitat and (ii) identify the soil properties and processes that contribute most to U and Th bioavailability in this system. We collected composite samples of plant leaves and stems, and samples from surface (AE) horizons and from the upper part of the Bs horizon at two sites. Concentration ratios (CRs) for U and Th were calculated for all plant tissues, using both the AE and Bs horizons as the base. Soil concentrations of U ranged from 16 to 25 microg g(-1), with a mean of 21.1 microg g(-1). Soil concentrations of Th ranged from 14 to 97 microg g(-1), with a mean of 41.8 microg g(-1). Mean U concentrations were 8.65 x 10(-3) microg g(-1) in leaf tissue, and 7.95 x 10(-3) microg g(-1) in stem tissue. Mean Th concentrations were 1.59 x 10(-1) microg g(-1) in leaf tissue, and 9.10 x 10(-2) microg g(-1) in stem tissue. Blueberry plants are cycling both U and Th in this system, with Th cycling occurring to a greater extent than U. In addition, Th was translocated preferentially to plant leaves while U concentrations showed little preferential translocation. Uranium uptake, however, seemed more sensitive than Th uptake to soil properties.     

Changes in soil quality and below-ground carbon storage with conversion of traditional agricultural crop lands to bioenergy crop production

Berm-isolated (0.5 ha) plots have been used since 1995 to quantify changes in soil and water quality with conversion from agricultural to bioenergy crops. Soil quality improvements, including increases in soil carbon storage, have occurred on sites planted to woody or herbaceous species, and no-till corn compared with tilled corn or cotton. Initial increases in soil carbon occurred within the upper 10 cm of the soil profile. Soil carbon on plantings of switchgrass, no-till corn, and sweetgum with a cover crop between the rows increased over the first 3 years. Soil carbon decreased by 6% on the sweetgum plantings without a cover crop and remained lower through the fifth growing season. Overall, the greatest increases in below ground carbon storage have occurred primarily within the upper 40 cm. Former land use, growth characteristics, management practices, and soil characteristics appear to be the primary factors determining the timing, depth. and extent of changes in soil carbon storage for bioenergy and no-till crops.